催化动力学分析法测定超痕量钒的研究

在稀磷酸介质及活化剂抗坏血酸存在下,痕量钒(Ⅴ)强烈催化溴酸钾氧化碱性品红褪色,据此建立了一个新的测定超痕量钒的催化动力学光度法.方法测定钒(Ⅴ)的线性范围为:0.0～400.0 pg/mL,检出限为27 pg/mL.实验考察了影响催化反应速率的各种因素,确定了实验的最佳条件.测定了催化反应的动力学参数:表观活化能E0'=170.1 kJ/mol,表观速率常数k'=2.8×10-3s-1,建立了动力学速率方程:-dCMR/dt=K'.CMR.CKBrO3.CVc.CV(Ⅴ).试验了25种共存离子的影响,发现大多数常见离子不干扰,方法直接用于环境水体中超痕量钒的测定,相对标准偏差为1.65%～2.03%.     

H2O2-天青Ⅱ催化动力学光度法测定痕量铜(Ⅱ)

在氨水介质中及加热条件下,痕量铜(Ⅱ)对H2O2氧化天青Ⅱ的褪色反应具有强烈的催化作用.探讨了最佳实验条件,据此建立了催化动力学光度法测定痕量铜(Ⅱ)的新方法.在选定的实验条件下,非催化反应与催化反应的吸光度差值△A与铜(Ⅱ)离子的质量浓度在16～56 μg/L范围内有良好的线性关系,检出限为9.36×10-11 g/mL.并且测定了催化反应的动力学参数,反应为准一级反应.在75℃下的表观速率常数为K'=4.04×10-3 8-1,表观活化能为74.54 kJ/mol.方法用于人发中痕量铜(Ⅱ)的测定,回收率在99.7%～100.0%之间.     

丽春红2R-溴酸钾催化光度法测定痕量钒

在硫酸介质和有抗坏血酸作活化剂的条件下,痕量钒(Ⅴ)能显著催化溴酸钾氧化丽春红2R(PR)的褪色反应。研究了该催化反应的最佳反应条件和动力学参数,建立了测定中草药及食品中痕量钒的催化动力学方法。线性范围为2.0~80ng/25mL,检出限为8.7×10-8g.L-1。     

亚甲基蓝-高碘酸钾催化动力学光度法测定痕量钌(Ⅲ)

在稀H_2SO_4介质中及加热85℃的条件下,钌(Ⅲ)对KIO_4氧化亚甲基蓝的褪色反应具有显著的催化作用,建立了一个催化动力学光度法测定痕量钌(Ⅲ)的新分析方法.探讨了该催化反应的最佳实验条件.非催化反应吸光度A_0与催化反应吸光度A之间的差值△A与钌(Ⅲ)质量浓度ρ在0～0.06μg/mL范围内呈良好的线性关系,检出限为2.37×10~(-10)g/mL.测定了动力学参数,反应为准一级反应,表观速率常数为3.63×10~(-4)/s,表观活化能为58.13 kJ/mol.对1.0μg Ru(Ⅲ)测定的相对标准偏差RSD为1.7%(n=11).方法用于分子筛样品中痕量钌(Ⅲ)的测定,回收率98.3%.     

催化动力学光度法测定钒尾矿中痕量钒(Ⅴ)

基于硫酸-柠檬酸钠介质中,钒(Ⅴ)催化H2O2氧化甲基绿的显色反应,建立了测定痕量钒(Ⅴ)的光度分析新方法。确定了催化褪色反应测定钒(Ⅴ)的动力学条件,催化反应的表观活化能E′a=83.34kJ/mol,反应速率常数K′=2.25×10-4/s。方法线性范围为0.20～80μg/L,检出限为0.88μg/L。方法的表观摩尔吸光系数ε=3.31×105L/(mol·cm)。用于本地钒尾矿中钒含量的测定,相对标准偏差为2.2%～2.9%,标准加入回收率为98.8%～102.9%。     

铼(Ⅶ)催化Na_2TeO_4与SnCl_2氧化还原反应及其应用研究

研究了在硫酸介质中,铼催化碲酸和氯化亚锡的氧化还原反应速率,建立了催化动力学光度法测定痕量铼的方法,优化了高铼酸钾-柠檬酸-碲酸钠-聚乙烯醇-二氯化锡反应的实验条件;测定了催化反应的表观活化能Ea'=15.87 kJ/mul和表观速率常数K'=1.28×10-3s-1,铼含量在0.004～1.2μg/mL范围内服从比尔定律.回归方程Y=0.129 cμg/10mL+0.016 3;相关系数r=0.997;应用于钼灰、钼精砂等矿样中铼的测定,测定结果的RSD≤±5%(n=5),加标回收率为98.0%～100.1%(n=5),符合实用性要求.     

甲基绿-高碘酸钾系统催化动力学光度法测定痕量铱(Ⅳ)

基于以H3PO4为反应介质,用HAc-NaAc(1+8)(pH5.7)作缓冲溶液,在沸水浴中加热条件下,痕量铱(Ⅳ)能灵敏地催化高碘酸钾氧化甲基绿的褪色反应,建立了一种测定痕量铱(Ⅳ)的新催化光度法。研究了反应的最佳条件。催化反应吸光度A与非催化反应吸光度A0的差值ΔA与铱(Ⅳ)的质量浓度ρ在0～2.0μg/25mL范围内呈良好的线性关系。检出限为2.97×10-10g/mL。对1μg/25mL铱(Ⅳ)测定的相对标准偏差为1.7%(n=11)。测定了动力学参数。该催化反应对铱(Ⅳ)为一级反应,总反应为准一级反应。反应的表观速率常数为4.613×10-4/s,表观活化能为40.56kJ/mol。该方法用于分子筛样品和活性炭中痕量铱(Ⅳ)的测定,回收率97.9%～104.4%。     

Rh(Ⅲ)-KIO4-孔雀绿体系催化动力学光度法测定痕量铑

在HCl介质及加热95 ℃的条件下,Rh(Ⅲ)对KIO4氧化孔雀绿的褪色反应有明显的催化作用,研究了指示反应的最佳反应条件和动力学参数,据此建立了催化动力学光度法测定痕量铑的新方法.非催化反应吸光度A0与催化反应吸光度A之间的差值ΔA与Rh(Ⅲ)质量浓度在0.004～0.060 μg/mL范围内具有良好的线性关系,检出限为5.98×10-10 g/mL.反应为准一级反应,表观速率常数为7.67×10-4 s-1,表观活化能为58.20 kJ/mol.该方法用于分子筛催化剂和活性炭中痕量铑的测定,回收率在95.8%～106.6%之间,符合痕量分析测定的要求.     

钒(Ⅴ)催化氧化二甲基黄的反应及其应用

在硫酸介质中 ,以抗坏血酸为活化剂 ,钒 (Ⅴ )强烈催化溴酸钾氧化二甲基黄的反应 ,由此建立了测定超痕量钒的又一新的催化光度法。方法的测定范围为 0 .8～ 10 0 pg·ml- 1,检出限为8.3× 10 - 13g·ml- 1,催化反应的表观活化能E′ =10 0 .2kJ·mol- 1,表观速率常数K =1.4× 10 - 3s- 1。方法用于井水、粮食中痕量钒的测定 ,结果满意。     

催化动力学光度法测定痕量钒(Ⅴ)的研究

在乙酸介质中,痕量钒(Ⅴ)对过硫酸钾氧化1 (2 吡啶偶氮)\|2 萘酚(PAN)褪色的指示反应有灵敏的催化作用。研究了该催化反应的最佳实验条件和动力学参数,建立了一种测定痕量钒(Ⅴ)的新方法,其线性范围为0.0～40.0μg/L钒(Ⅴ),方法检出限为2.62×10-9g/mL。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.